TW202142633A - Coating compositions and methods of forming electronic devices - Google Patents

Abstract

Coating compositions comprise: a curable compound comprising: a core chosen from a C₆ carbocyclic aromatic ring, a C_2‑5 heterocyclic aromatic ring, a C_9-30 fused carbocyclic aromatic ring system, a C_4‑30 fused heterocyclic aromatic ring system, C_1‑20 aliphatic, and C_3-20 cycloaliphatic, and three or more substituents of formula (1)

wherein at least two substituents of formula (1) are attached to the aromatic core; and wherein: Ar¹ is chosen from a C₆ carbocyclic aromatic ring, a C_2‑5 heterocyclic aromatic ring, a C_9-30 fused carbocyclic aromatic ring system, and a C_4‑30 fused heteroocyclic aromatic ring system; Z is a substituent independently chosen from OR¹ , protected hydroxyl, carboxyl, protected carboxyl, SR¹ , protected thiol, ‑O‑C(=O)-C_1-6 alkyl, halogen, and NHR² ; wherein each R¹ is independently chosen from H, C_1-10 alkyl, C_2-10 unsaturated hydrocarbyl, and C_5-30 aryl; each R² is independently chosen from H, C_1-10 alkyl, C_2-10 unsaturated hydrocarbyl, C_5-30 aryl, C(=O)-R¹ , and S(=O)₂ -R¹ ;x is an integer from 1 to the total number of available aromatic ring atoms in Ar¹ ; and * denotes the point of attachment to the core; provided that no substituents of formula (1) are in an ortho position to each other on the same aromatic ring of the core; a polymer; and one or more solvents, wherein the total solvent content is from 50 to 99 wt% based on the coating composition. Coated substrates formed with the coating compositions and methods of forming electronic devices using the compositions are also provided. The compositions, coated substrates and methods find particular applicability in the manufacture of semiconductor devices.

Description

Coating composition and method of forming electronic device

The present invention relates generally to the field of electronic device manufacturing, and more specifically to the field of coating compositions for manufacturing electronic devices such as semiconductor devices.

It is well known in the photolithography process that if the resist pattern is relatively high relative to its width (high aspect ratio), the resist pattern may collapse due to the surface tension from the developer used. Multi-layer resist processes (such as three-layer and four-layer processes) have been designed, which can solve the problem of pattern collapse when a high aspect ratio is desired. This type of multilayer process uses a top layer of resist, one or more intermediate layers, and a bottom layer (or underlayer). In such a multilayer resist process, the top photoresist layer is imaged and developed in a typical manner to provide a resist pattern. The pattern is then transferred to one or more intermediate layers, typically by etching. Each intermediate layer is selected so that a different etching process is used, such as different plasma etching. Finally, the pattern is transferred to the bottom layer, typically by etching. Such an intermediate layer can be composed of a variety of materials, but the bottom layer material is typically composed of a high carbon content material. The underlying material is selected to provide the desired anti-reflection characteristics, planarization characteristics, and etch selectivity.

Prior technologies used for underlayer formation include chemical vapor deposition (CVD) carbon and solution-processed high carbon content polymers. CVD materials have several significant limitations, including high cost of ownership, inability to form a planarization layer on the topography of the substrate, and high absorbance for pattern alignment at 633 nm. For these reasons, the industry has turned to solution-processed high-carbon content materials as the bottom layer. The underlying material should ideally meet the following characteristics: it can be cast onto the substrate by a spin coating process; it is heat-set when heated, with low outgassing and sublimation; it can be dissolved in common processing solvents with good equipment compatibility; The n and k values are combined with the currently used silicon hard mask and the bottom anti-reflective (BARC) layer to give the photoresist the necessary low reflectivity for imaging; it is thermally stable up to> 400°C for subsequent It is not damaged during the manufacturing process (for example, CVD such as silicon oxynitride (SiON) CVD process); and resists the removal of the photoresist or other common solvents used in the over-coated photoresist.

其中R₁ 、R₂ 和R₃ 各自獨立地表示式R^A -C≡C-R^B -，其中R^A 尤其可以是被羥基和芳基中的至少一種取代的芳基，並且R^B 係單鍵或芳基，其中此類化合物可用於形成半導體裝置製造中的底層。然而，此類化合物在相對高溫度下固化。It is well known that materials with relatively low molecular weight have relatively low viscosity and can flow into topography in the substrate such as vias and trenches to provide a planarization layer. The underlying material must be able to be flattened with relatively low outgassing up to 400°C. For use as a high carbon content underlayer, it is desirable that any composition is heat set when heated. U.S. Patent No. 9,581,905 B2 discloses a compound having the formula

Wherein R ₁ , R ₂ and R ₃ each independently represent the formula R ^A -C≡CR ^B -, wherein R ^A may especially be an aryl group substituted by at least one of a hydroxyl group and an aryl group, and R ^B is a single bond or Aryl groups, where such compounds can be used to form the bottom layer in the manufacture of semiconductor devices. However, such compounds cure at relatively high temperatures.

There is a need in the art for coating compositions that can be used to form electronic devices, and methods for using such compositions, which solve one or more problems related to the prior art.

(1) 其中至少兩個具有式 (1) 的取代基附接到該芳香族核；並且其中：Ar¹ 選自C₆ 碳環芳香族環、C_2-5 雜環芳香族環、C_9-30 稠合碳環芳香族環系統、和C_4-30 稠合雜環芳香族環系統；Z係獨立地選自以下的取代基：OR¹ 、受保護的羥基、羧基、受保護的羧基、SR¹ 、受保護的巰基、-O-C(=O)-C_1-6 烷基、鹵素、和NHR² ；其中每個R¹ 獨立地選自H、C_1-10 烷基、C_2-10 不飽和烴基、和C_5-30 芳基；每個R² 獨立地選自H、C_1-10 烷基、C_2-10 不飽和烴基、C_5-30 芳基、C(=O)-R¹ 、和S(=O)₂ -R¹ ；x 係1至Ar¹ 中可用芳香族環原子總數的整數；並且*指示與該核的附接點；前提係在該核的同一芳香族環上具有式 (1) 的取代基彼此不處於鄰位；聚合物；以及一種或多種溶劑，其中總溶劑含量係基於該塗層組成物的50至99 wt%。According to the first aspect of the present invention, a coating composition is provided. The coating composition includes: a first curable compound, the first curable compound includes: an aromatic nucleus, the aromatic nucleus is selected from C ₆ carbocyclic aromatic ring, C _2-5 heterocyclic aromatic ring, C _{9-30 condensed carbocyclic aromatic ring} system, and C _{4-30 condensed heterocyclic aromatic ring} system; and three or more substituents having formula (1)

(1) wherein at least two substituents having formula (1) are attached to the aromatic core; and wherein: Ar ^{1 is} selected from C ₆ carbocyclic aromatic ring, C _2-5 heterocyclic aromatic ring, C _{9 -30} fused carbocyclic aromatic ring system, and C _4-30 fused heterocyclic aromatic ring system; Z is independently selected from the following substituents: OR ¹ , protected hydroxyl, carboxy, protected carboxy , SR ¹ , protected mercapto, -OC(=O)-C _1-6 alkyl, halogen, and NHR ² ; wherein each R ^{1 is} independently selected from H, C _1-10 alkyl, C _{2- 10} unsaturated hydrocarbon groups, and C _5-30 aryl groups; each R ^{2 is} independently selected from H, C _1-10 alkyl groups, C _2-10 unsaturated hydrocarbon groups, C _5-30 aryl groups, C(=O) -R ¹ , and S(=O) ₂ -R ¹ ; x is an integer from 1 to the ^{total number of aromatic ring atoms available in Ar 1} ; and * indicates the point of attachment to the nucleus; the premise is the same aromatic in the nucleus The substituents having formula (1) on the group ring are not in the ortho position to each other; polymers; and one or more solvents, wherein the total solvent content is based on 50 to 99 wt% of the coating composition.

According to another aspect of the present invention, a coated substrate is provided. The coated substrate includes: an electronic device substrate; and a layer formed of the coating composition as described herein on the surface of the electronic device substrate. The layer can function in one or more capabilities, for example, as a photoresist bottom layer, a planarization layer, a gap fill layer, a protective layer, or a combination thereof.

According to another aspect of the present invention, a method of forming an electronic device is provided. The method includes: (a) providing an electronic device substrate; (b) coating a layer of the coating composition as described herein on the surface of the electronic device substrate; and (c) curing the layer of curable compound to A cured layer is formed. In another aspect of the method, the cured layer can be used as a photoresist bottom layer in a patterning process. The method further includes: (d) forming a photoresist layer on the bottom layer; (e) exposing the photoresist layer to activating radiation in a pattern; (f) making the exposed photoresist The agent layer is developed to form a pattern in the photoresist layer; and (g) the pattern is transferred to the bottom layer. In another aspect of the method, one or more of a silicon-containing layer, an organic anti-reflective coating, or a combination thereof may be coated on the bottom layer before step (d). On the other hand, after step (f) and before step (g), the pattern can be transferred to one or more of the silicon-containing layer, the organic anti-reflective coating, or a combination thereof. In yet another aspect, the method may further include: (h) transferring the pattern to a layer of the electronic device substrate below the patterned underlayer; and (i) removing the patterned underlayer.

It will be understood that when an element is referred to as being "on or over" another element, it can be directly adjacent to another element or intervening elements that may be present therebetween. In contrast, when an element is said to be "directly on" another element, there is no intervening element. As used herein, the term "and/or" includes any and all combinations of one or more of the related listed items.

It will also be understood that although the terms first, second, third, etc. may be used herein to describe different elements, elements, regions, layers and/or sections, these elements, elements, regions, layers and/or Parts should not be restricted by these terms. These terms are only used to distinguish one element, element, region, layer or section from another element, element, region, layer or section. Therefore, the first element, element, region, layer or section discussed below may be referred to as a second element, element, region, layer or section without departing from the teachings of the present invention.

As used throughout this specification, unless the context clearly indicates otherwise, the following abbreviations shall have the following meanings: °C = degrees Celsius; g = grams; mg = milligrams; L = liters; mL = milliliters; Å = angstroms; nm = Nanometers; µm = micron = micrometer; mm = millimeters; sec. = seconds; min. = minutes; hr. = hours; DI = deionized; and Da = Dalton. Unless otherwise specified, "wt%" refers to a weight percentage based on the total weight of the reference composition.

Unless otherwise indicated, "aliphatic," "aromatic," "alkyl," and "aryl" include heteroaliphatic, heteroaromatic, heteroalkyl, and heteroaryl, respectively. The terms "heteroaliphatic", "heteroaromatic", "heteroalkyl", "heteroaryl", etc. respectively refer to the substitution of one or more heteroatoms (such as nitrogen, oxygen, sulfur, phosphorus or silicon) Aliphatic, aromatic, alkyl and aryl groups of one or more carbon atoms within, for example, as in ethers or thioethers.

Unless otherwise specified, "aliphatic" refers to open-chain (straight or branched) and cyclic aliphatics. The aliphatic structure can be saturated (e.g., alkanes) or unsaturated (e.g., alkenes or alkynes). Aliphatic refers to aliphatic groups, and includes aliphatic monovalent groups, divalent groups, and higher valent groups. Unless otherwise indicated, "aliphatic" includes "heteroaliphatic". In a preferred aspect, the aliphatic group does not contain heteroatoms.

Unless otherwise specified, "alkyl" refers to linear, branched, and cyclic alkyl groups. As used herein, "alkyl" refers to an alkane group, and includes alkane monovalent groups, divalent groups (alkylene groups), and higher valent groups. Unless otherwise indicated, "alkyl" includes "heteroalkyl". In a preferred aspect, the alkyl group does not contain heteroatoms. If the number of carbons is not indicated for any alkyl or heteroalkyl group, then 1-12 carbons are expected.

"Aromatic" and "aryl" include aromatic carbocyclic and aromatic heterocyclic rings. The terms "aromatic" and "aryl" refer to aromatic groups, and include monovalent groups, divalent groups (arylene groups), and higher valence groups. In a preferred aspect, the aromatic or aryl group is an aromatic carbocyclic ring.

Unless otherwise specified, "substituted" refers to a moiety whose one or more hydrogens are replaced by one or more substituents selected from the group consisting of halogen, C _1-6 alkyl, halo-C _1-6 alkyl , C _1-6 alkoxy, halo-C _1-6 alkoxy, phenyl, and phenoxy, preferably selected from halogen, C _1-6 alkyl, halo-C _1-4 Alkyl, C _1-6 alkoxy, halo-C ₁₄ alkoxy, and phenyl, and more preferably selected from halogen, C _1-6 alkyl, C _1-6 alkoxy, Phenyl, and phenoxy. Unless otherwise specified, the substituted moiety preferably has 1 to 3 substituents, and more preferably 1 or 2 substituents. "Halo" refers to fluorine, chlorine, bromine and iodine.

The term "B-stage" refers to the partially cured reaction product of a specific compound or compounds. As used herein, "partially cured" refers to a reaction product that is in the form of an oligomer and can be further polymerized or cured to form a higher molecular weight material, such as when a coating composition is coated on a substrate and cured to form the composition The layer or film is the available reaction product. When such a coating composition is applied on a substrate to form a film, such a partially cured reaction product can undergo further curing during subsequent processing steps.

"Oligomer (Oligomer and oligomeric)" refers to a low molecular weight polymer that includes a small amount (for example, 2 to 10) of total units and can be further cured. As used herein, the term "polymer" includes oligomers. The term "curing" means any process that increases the total molecular weight of the material, removes the solubility-enhancing group, or both increases the total molecular weight and removes the solubility-enhancing group, such as polymerization or condensation. "Curable" refers to any material that can be cured under certain conditions. As used herein, "gap" refers to any hole in a semiconductor substrate that is intended to be filled with a gap-filling composition.

The article "a/an" refers to both the singular and the plural. Unless otherwise indicated, all amounts are percentages by weight and all ratios are by weight. All numerical ranges are inclusive and can be combined in any order, except when it is obvious that such numerical ranges are limited to add up to a maximum of 100%.

(1) 其中至少兩個具有式 (1) 的取代基附接到該核；並且其中：Ar¹ 選自C₆ 碳環芳香族環、C_2-5 雜環芳香族環、C_9-30 稠合碳環芳香族環系統、和C_4-30 稠合雜環芳香族環系統；Z係獨立地選自以下的取代基：OR¹ 、受保護的羥基、羧基、受保護的羧基、SR¹ 、受保護的巰基、-O-C(=O)-C_1-6 烷基、鹵素、和NHR² ；其中每個R¹ 獨立地選自H、C_1-10 烷基、C_2-10 不飽和烴基、和C_5-30 芳基；每個R² 獨立地選自H、C_1-10 烷基、C_2-10 不飽和烴基、C_5-30 芳基、C(=O)-R¹ 、和S(=O)₂ -R¹ ；x 係1至Ar¹ 中可用芳香族環原子總數的整數；並且*指示與該核的附接點；前提係在該核的同一芳香族環上具有式 (1) 的取代基彼此不處於鄰位。因此，與該核的同一芳香族環鍵合的具有式 (1) 的取代基將不與芳香族環的緊鄰的碳原子鍵合，例如在苯核的1位和2位處。The coating composition of the present invention comprises a curable compound, and the curable compound comprises: a core selected from the group consisting of a C ₆ carbocyclic aromatic ring, a C _2-5 heterocyclic aromatic ring, and a C _{9-30 condensed carbocyclic ring Aromatic ring} system, C _{4-30 condensed heterocyclic aromatic ring} system, C _1-20 aliphatic, and C _3-20 alicyclic; and three or more substituents having formula (1)

(1) wherein at least two substituents having formula (1) are attached to the core; and wherein: Ar ^{1 is} selected from C ₆ carbocyclic aromatic ring, C _2-5 heterocyclic aromatic ring, C _9-30 Condensed carbocyclic aromatic ring system, and C _4-30 condensed heterocyclic aromatic ring system; Z is independently selected from the following substituents: OR ¹ , protected hydroxyl, carboxy, protected carboxy, SR ^1. Protected mercapto, -OC(=O)-C _1-6 alkyl, halogen, and NHR ² ; wherein each R ^{1 is} independently selected from H, C _1-10 alkyl, C _2-10 Saturated hydrocarbon group, and C _5-30 aryl group; each R ^{2 is} independently selected from H, C _1-10 alkyl group, C _2-10 unsaturated hydrocarbon group, C _5-30 aryl group, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x is an integer from 1 to the ^{total number of aromatic ring atoms available in Ar 1} ; and * indicates the point of attachment to the nucleus; the premise is on the same aromatic ring of the nucleus The substituents having the formula (1) above are not in the ortho position to each other. Therefore, the substituents of formula (1) that are bonded to the same aromatic ring of the nucleus will not bond to the immediately adjacent carbon atoms of the aromatic ring, such as at the 1 and 2 positions of the benzene nucleus.

Preferably, each Z is independently selected from OR ¹ , protected hydroxy, carboxy, protected carboxy, SH, -OC(=0)-C _1-6 alkyl, and NHR ² . More preferably, each Z is independently selected from hydroxyl, protected hydroxyl, OCH ₂ C≡CH, carboxy, protected carboxy, and NHR ² , and more preferably, is selected from hydroxyl, protected Hydroxy, OCH ₂ C≡CH, carboxy, and protected carboxy are still more preferably selected from hydroxyl and protected hydroxyl, and most preferably are selected from hydroxyl. Each R ^{1 is} independently selected from H, C _1-10 alkyl, C _2-10 unsaturated hydrocarbon group, and C _5-30 aryl group, and is more preferably selected from H, C _1-10 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, and C _5-30 aryl. In a preferred embodiment, R ¹ is H. Each R ^{2 is} independently selected from H, C _1-10 alkyl, C _2-10 unsaturated hydrocarbyl, C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ . Preferably, R ^{2 is} selected from H, C _1-10 -alkyl, C _2-10 -unsaturated hydrocarbon group, and C _5-30 aryl group, and more preferably is selected from H, C _1-10 -Alkyl, C _2-10 -alkenyl and C _2-10 -alkynyl.

。 _{As used herein, the term "core" refers to a C 6} carbocyclic aromatic ring, C _2-5 heterocyclic ring having a moiety of formula (1) attached thereto, and preferably 2 to 6 Aromatic ring, C _{9-30 condensed carbocyclic aromatic ring} system, C _{4-30 condensed heterocyclic aromatic ring} system, C _1-20 aliphatic, and C _3-20 alicyclic. It should be understood that, in the compound from which the curable compound is formed, the nucleus described below (for example, pyridine, benzene...) is substituted with a substituent of formula (1) and optional additional substituents as described above . For example, the following compounds should be understood as having a benzene nucleus and 3 substituents having formula (1):

.

The nucleus is preferably a C ₆ carbocyclic aromatic ring, a C _2-5 heterocyclic aromatic ring, a C _{9-30 condensed carbocyclic aromatic ring} system, or a C _{4-30 condensed heterocyclic aromatic ring} system. Suitable aromatic nuclei include, for example, those selected from the group consisting of pyridine, benzene, naphthalene, quinoline, isoquinoline, carbazole, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, vinegar, benzene And [a]anthracene, dibenzo[a,h]anthracene, azole, isoazole, thiazole, isothiazole, triazole, and benzo[a]pyrene, more preferably selected from benzene, naphthalene, Carbazole, anthracene, phenanthrene, pyrene, coronene, triphenanthrene, chrysene, anthracene, benzo[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and more preferably It is selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenanthrene, chrysene, and vine. The aliphatic core can be substituted or unsubstituted, linear, branched or cyclic, and saturated or unsaturated (alkanes, alkenes or alkynes). Suitable aliphatic cores and heteroaliphatic cores include, for example, those selected from the group consisting of methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, methylmethane , Dimethyl methane, dimethyl ether, butene, butyne, dimethyl sulfide, trimethylamine and tetramethyl silane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclo Octane, cyclononane, cyclodecane, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1, 5-cyclooctadiene, norbornene, adamantane, tetrahydropiperan, tetrahydrothiophene, pyrrolidine, tetrahydro-2H-piperan, tetrahydro-2H-thiopyran, piperidine and dipyran.

In formula (1), preferably, each Ar ^{1 is} independently selected from the group consisting of pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, phenanthrene, pyrene, benzene And [a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, more preferably selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, anthracene , Benzo[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and even more preferably selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene , Qi, and 萉. Preferably, x =1 or 2, and more preferably x =1.

The curable compound has three or more substituents having formula (1), of which two or more substituents having formula (1) are directly attached to the core. It is further preferred that the curable compound has 2 to 4 substituents having the formula (1) attached to the core, and more preferably 3 having the formula (1) attached to the core part. One or more substituents having formula (1) may also be present in the curable compound, but are not directly attached to the core. The curable compound may have any suitable number of moieties of formula (1), such as 2 to 10, preferably 2 to 8, more preferably 2 to 6, and even more preferably 3 or 4. . When the nucleus contains an aromatic ring, the substituents having the formula (1) on the same aromatic ring of the nucleus are not in the ortho position to each other.

(2) 其中：R⁰ 係如上所述之核，並且選自C₆ 碳環芳香族環、C_2-5 雜環芳香族環、C_9-30 稠合碳環芳香族環系統、C_4-30 稠合雜環芳香族環系統、C_1-20 脂肪族、和C_3-20 脂環族；Ar¹ 、Ar² 、和Ar³ 各自獨立地是芳香族基團，其獨立地選自C₆ 碳環芳香族環、C_2-5 雜環芳香族環、C_9-30 稠合碳環芳香族環系統、和C_4-30 稠合雜環芳香族環系統；Y係共價化學單鍵、二價連接基團、或三價連接基團；Z¹ 和Z² 獨立地選自OR¹ 、受保護的羥基、羧基、受保護的羧基、SR¹ 、受保護的巰基、-O-C(=O)-C_1-6 -烷基、鹵素、和NHR² ；每個R¹ 選自H、C_1-10 烷基、C_2-10 不飽和烴基、和C_5-30 芳基；每個R² 選自H、C_1-10 烷基、C_2-10 不飽和烴基、C_5-30 芳基、C(=O)-R¹ 、和S(=O)₂ -R¹ ；x1 = 1至4；x2 = 1至4；y1 = 2至4；每個y2 = 0至4；y1 + 每個y2 ≥ 2；w = 0至2；並且z 等於0至2；其中當Y係共價化學單鍵或二價連接基團時，z = 1；並且當Y係三價連接基團時， z = 2。The curable compound useful in the coating composition of the present invention preferably has the formula (2)

(2) Wherein: R ⁰ is the nucleus as described above, and is selected from C ₆ carbocyclic aromatic ring, C _2-5 heterocyclic aromatic ring, C _9-30 condensed carbocyclic aromatic ring system, C _{4 -30} fused heterocyclic aromatic ring system, C _1-20 aliphatic, and C _3-20 alicyclic; Ar ¹ , Ar ² , and Ar ³ are each independently an aromatic group, which is independently selected from C ₆ carbocyclic aromatic ring, C _2-5 heterocyclic aromatic ring, C _9-30 fused carbocyclic aromatic ring system, and C _4-30 fused heterocyclic aromatic ring system; Y series covalent chemistry Single bond, divalent linking group, or trivalent linking group; Z ¹ and Z ^{2 are} independently selected from OR ¹ , protected hydroxyl, carboxy, protected carboxy, SR ¹ , protected sulfhydryl, -OC (=O)-C _1-6 -alkyl, halogen, and NHR ² ; each R ^{1 is} selected from H, C _1-10 alkyl, C _2-10 unsaturated hydrocarbon group, and C _5-30 aryl group; Each R ^{2 is} selected from H, C _1-10 alkyl, C _2-10 unsaturated hydrocarbon group, C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x1 = 1 to 4; x2 = 1 to 4; y1 = 2 to 4; each y2 = 0 to 4; y1 + each y2 ≥ 2; w = 0 to 2; and z is equal to 0 to 2; where Y When it is a covalent chemical single bond or a divalent linking group, z =1; and when Y is a trivalent linking group , z =2.

Preferably, R ⁰ is an aromatic nucleus having 5 to 30 carbon atoms, and more preferably 5 to 20 carbon atoms. Suitable aromatic nuclei for R ⁰ include, but are not limited to, pyridine, benzene, naphthalene, quinoline, isoquinoline, carbazole, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, anthracene, benzo[a]anthracene A ]Anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and more preferably benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenanthrene, phenanthrene, and anthracene. Suitable aliphatic nuclei include, for example, those selected from the group consisting of methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, methylmethane, dimethylmethane , Dimethyl ether, butene, butyne, dimethyl sulfide, trimethylamine, and tetramethylsilane. Suitable cycloaliphatic nuclei include, for example, those selected from the group consisting of cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclopropene, cyclopropane Butene, cyclopentene, cyclohexene, cycloheptene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, adamantane, tetrahydropiperan, Tetrahydrothiophene, pyrrolidine, tetrahydro-2H-piperan, tetrahydro-2H-thiopyran, piperidine, and dipyridine.

Ar ¹ , Ar ² , and Ar ^{3 are} preferably each independently selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, phenanthrene, vine, benzo[ a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, more preferably selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenanthrene, pyrene, vinegar, benzene And [a] anthracene, dibenzo [a, h] anthracene, and benzo [a] pyrene, and more preferably selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, phenanthrene , And 萉. More preferably, R ^{0 is} selected from the group consisting of pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylphenanthrene, triphenylene, pyrene, benzo[a]anthracene, dibenzo[ a,h]anthracene, and benzo[a]pyrene, and Ar ¹ , Ar ² , and Ar ³ are each independently selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, Triphenanthrene, chrysene, anthracene, benzo[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene. Preferably, Z ¹ and Z ² are each independently selected from OR ¹ , protected hydroxy, carboxy (C(=O)OH), protected carboxy, SH, fluorine, and NHR ² , more preferably Is selected from hydroxyl (OH), protected hydroxyl, OCH ₂ C≡CH, C(=O)OH, protected carboxyl, and NHR ² , and more preferably selected from OH, protected hydroxyl, OCH ₂ C≡CH, a carboxyl group, and a protected carboxyl group, and still more preferably are selected from OH and a protected hydroxyl group. Each R ^{1 is} independently selected from H, C _1-10 alkyl, C _2-10 unsaturated hydrocarbon group, and C _5-30 aryl, and is more preferably selected from H, C _1-10 -alkyl , C _2-10 -alkenyl, C _2-10 -alkynyl, and C _5-30 aryl. In a preferred embodiment, R ¹ is H. Preferably, R ^{2 is} selected from H, C _1-10 -alkyl, C _2-10 -unsaturated hydrocarbon group, and C _5-30 -aryl, and more preferably is selected from H, C _{1- 10} -alkyl, C _2-10 -alkenyl and C _2-10 -alkynyl. Preferably, each Z ¹ is the same. It is also preferred that each Z ² is the same. More preferably, Z ¹ = Z ² . Preferably, x1 and x2 are each independently selected from 1 to 3, more preferably independently 1 or 2, and still more preferably each is 1. Preferably, each y2 =0 to 2. Preferably, y1 + each y2 = 3 to 8, more preferably 3 to 6, and still more preferably 3 or 4. Preferably, w =0 to 1. In a preferred embodiment, when w =0, R ⁰ and each Ar ¹ are not phenyl groups. In a preferred embodiment, Y is a covalent single bond. In another preferred embodiment, Y is a divalent or trivalent linking group. Exemplary linking groups for Y include but are not limited to O, S, N(R ³ ) _r , S(=0) ₂ , CR ⁴ R ⁵ , bis-imine moiety, bis-etherimine moiety, bis -Ketoimid moiety, bis-benzoxazole moiety, bis-benzimidazole moiety, and bis-benzothiazole moiety, wherein r =0 or 1, and preferably the linking group of Y is O, N(R ³ ) _w , and CR ⁴ R ⁵ . R ³ is **-C(=O)-C _5-30 -aryl or **-S(=O) ₂ -C _5-30 -aryl, where ** is the attachment point to N. R ⁴ and R ^{5 are} independently selected from H, C _1-10 -alkyl and C _5-10 -aryl, and R ⁴ and R ⁴ may form a 5-membered or 6-membered ring together with the carbon to which they are attached, The ring may be fused with one or more aromatic rings.

(A) 其中*指示與R⁰ 和Ar² 的附接點。合適的Y的雙-醯亞胺部分連接基團由式 (B) 和式 (C) 示出，其中Y¹ 係共價單鍵或C_5-30 -伸芳基，其中*指示與R⁰ 和Ar² 的附接點。合適的雙-醚醯亞胺部分和雙-酮醯亞胺部分係具有式 (C) 的那些，其中分別地，Y¹ = O或-C(=O)-，並且其中*指示與R⁰ 和Ar² 的附接點。合適的雙-苯并㗁唑、雙-苯并咪唑、和雙-苯并噻唑部分係具有式 (D) 的那些，其中分別地，G = O、NH、和S，並且其中Y² 係共價單鍵或C_5-30 -伸芳基，並且其中*指示與R⁰ 和Ar² 的附接點。

(B)

(C)

(D)When Y = CR ⁴ R ⁵ , a suitable linking group has the stubby moiety of the following formula (A)

(A) Where * indicates the attachment point ^{with R 0} and Ar ^2. Suitable bis-imine moiety linking groups of Y are shown by formula (B) and formula (C), wherein Y ¹ is a covalent single bond or a C _{5-30 -arylene} group, where * indicates the same as R ⁰ And Ar ² attachment point. Suitable bis-ether imine moieties and bis-keto imine moieties are those having the formula (C), wherein Y ¹ = O or -C(=O)-, respectively, and wherein * indicates the same as R ⁰ And Ar ² attachment point. Suitable bis-benzoxazole, bis-benzimidazole, and bis-benzothiazole moieties are those of formula (D), where G = O, NH, and S, respectively, and where Y ² is a total Valence single bond or C _5-30 -aryl group, and where * indicates the point of attachment ^{to R 0} and Ar ^2.

(B)

(C)

(D)

^{For Z, Z 1} and Z ^{2 in} formulas (1) and (2), the protected carboxyl group is any group that can be cleaved (deprotected) under certain conditions to produce a carboxyl group. Such protected carboxyl groups can be deprotected by heat, acid, base or a combination thereof, preferably by heat, acid or a combination thereof, and more preferably by heat. Exemplary protected carboxy groups include esters such as benzyl esters and esters with a quaternary carbon directly bonded to the alkoxy oxygen of the ester group. Preferably, the protected carboxyl group is an ester having a quaternary carbon directly bonded to the alkoxy oxygen of the ester group, and more preferably the ester has the formula YC(O)-O-CR'R "R '", wherein Y-based organic residue, and R', R "and R"'are each independently selected from C ₁ - ₁₀ alkyl. Preferred protected carboxyl groups include: tertiary butyl ester; 1-alkylcyclopentyl esters such as 1-methylcyclopentyl ester and 1-ethylcyclopentyl ester; 2,3-dimethyl-2-butyl ester ; 3-Methyl-3-pentyl ester; 2,3,3-trimethyl-3-butyl ester; 1,2-dimethylcyclopentyl ester; 2,3,4-trimethyl-3-pentyl ester Esters; 2,2,3,4,4-pentamethyl-3-pentyl ester; and adamantyl esters such as hydroxyadamantyl ester and C _{1-12 alkyladamantyl} ester. Each of the above-mentioned protected carboxyl groups can be deprotected by one or more of heat, acid or base. Preferably, heat, acid, or a combination of heat and acid is used, and more preferably, the protected carboxyl group is deprotected by heat. For example, the protected carboxyl groups can be deprotected at a pH ≤ 4 and preferably ≤ 1. At this pH, the protected carboxyl group is typically heated to a temperature of, for example, 90°C to 110°C, and preferably about 100°C, to promote deprotection. Alternatively, when the protected carboxyl group is an ester having a tertiary carbon directly bonded to the alkoxy oxygen of the ester group, the protected carboxyl group can be deprotected by heating to a suitable temperature, such as ≥ 125°C, preferably 125°C to 250°C, and more preferably 150°C to 250°C. Such protected carboxyl groups and their use conditions are well known in the art. For example, US Patent No. 6,136,501 discloses various ester groups with quaternary carbons of alkoxy oxygen directly bonded to the ester group.

^{For Z, Z 1} and Z ^{2 in} formulas (1) and (2), a suitable protected hydroxyl group is any group that can be cleaved (deprotected) under certain conditions to produce a hydroxyl group. Such protected hydroxyl groups can be deprotected by heat, acid, base, or a combination thereof. Exemplary protected hydroxyl groups include: ethers such as methoxymethyl ether, ethoxyethyl ether, 2-methoxypropyl ether, tetrahydropiperanyl ether, tertiary butyl ether, allyl Ether, benzyl ether, tertiary butyl dimethyl silyl ether, tertiary butyl diphenyl silyl ether, acetonide, and benzyl acetal; esters such as trimethyl acetate and benzene Formate; and carbonates such as tertiary butyl carbonate. Each of the above-mentioned protected hydroxyl groups may be deprotected under acidic or basic conditions, and preferably under acidic conditions. More preferably, an acid or a combination of acid and heat is used to deprotect the protected hydroxyl group. For example, the protected hydroxyl groups can be deprotected at a pH ≤ 4 and preferably ≤ 1. At this pH, the protected hydroxyl group is typically heated to a temperature of, for example, 90°C to 110°C, and preferably about 100°C, to promote deprotection. Such protected hydroxyl groups and their use conditions are well known in the art.

^{For Z, Z 1} and Z ^{2 in} formulas (1) and (2), a suitable protected sulfhydryl group is any group that can be cleaved (deprotected) under certain conditions to produce a sulfhydryl group. Such protected sulfhydryl groups can be cleaved by heat, acid, base, or a combination thereof. Exemplary protected mercapto groups include: ethers such as methoxymethyl sulfide, tetrahydropiperanyl sulfide, tertiary butyl sulfide, allyl sulfide, benzyl sulfide, tertiary butyl disulfide Methylsilyl sulfide, tertiary butyl diphenylsilyl sulfide, thioacetone compound, and benzhydryl thioacetal; thioesters, such as trimethyl acetate thioester and benzoic acid thioester; and Thiocarbonates, such as tertiary butyl thiocarbonate. Each of the above-mentioned protected sulfhydryl groups may be deprotected under acidic or basic conditions, and preferably under acidic conditions. More preferably, an acid or a combination of acid and heat is used to deprotect the protected sulfhydryl group. For example, the protected sulfhydryl groups can be deprotected at room temperature, for example when exposed to a pH ≤1. At this pH, the protected sulfhydryl group is typically heated to a temperature of, for example, 90°C to 110°C, and preferably about 100°C, to promote deprotection. Such protected sulfhydryl groups and their use conditions are well known in the art.

The curable compound may be present in the coating composition in a wide range of, for example, 1 to 99 wt%, 10 to 99 wt%, or 50 to 90 wt% based on the total solids of the coating composition. It may be desirable that the curable compound is present in a relatively small amount relative to the total solids of the composition, for example, 1 to 50 wt% or 1 to 30 wt%.

The curable compound as described above can be easily manufactured by those skilled in the art using known synthesis techniques. For example, the compound can be prepared by mixing reactants (such as aryl halides or alkyl halides) with aromatic alkynes and one or more suitable catalysts (such as copper and palladium catalysts), a base, and a solvent. The solvent is typically an organic solvent, which is, for example, selected from toluene, benzene, tetrahydrofuran, dioxane, and combinations thereof. The reaction is carried out at a temperature and time effective to cause the reactants in the reaction mixture to react to form a curable compound. The reaction temperature is typically 0°C to 200°C, preferably 25°C to 100°C. The reaction time is typically 5 minutes to 96 hours, preferably 2 to 24 hours. The product compound can be purified by techniques known in the art (such as column chromatography).

。The coating composition further includes one or more polymers. The inclusion of a polymer in the coating composition may allow adjustment or improvement of one or more characteristics of the composition or the layer formed therefrom, for example, planarization performance, peel resistance, etching rate, or coating quality. Such characteristics can be adjusted by selecting a suitable polymer and adjusting the relative amounts of curable compound and polymer in the composition. Suitable polymers include, for example, those selected from acrylates, vinyl aromatic polymers, novolacs, polyphenylenes, polyarylene ethers, polyimines, polybenzoxazoles , Polybenzimidazole, polybenzothiazole, polyquinoline, polyether ether, B-stage reaction product of the above-mentioned curable compound, and combinations thereof. The polymer preferably contains one or more functional groups selected from, for example, hydroxyl, alkoxy, epoxy, alkenyl, alkynyl, carboxylic acid, acetal, ketal, tertiary alkyl ester and amine. Among these functional groups, epoxy groups are preferred. Suitable such polymers are known and can be easily manufactured by those skilled in the art using known synthesis techniques. Suitable polymers are described, for example, in the following: U.S. Patent Nos. 5349111 A, 5965679 A, 7303855 B2, 7749681 B2, 8674052 B2, 9244353 B2, and 9540476 B2; U.S. Patent Application Publication Nos. 2008/0160460 A1, 2013/0171569 A1 , 2013/0280913 Al and 2019/0146346 Al; DW Smith et al., Polyarylene Networks via Bergman Cyclopolymerization of Bis-ortho-diynyl Arenes [Polyarylene network via Bergman ring polymerization of di -ortho-diynyl arenes] , Adv .. Funct Mater [advanced materials] 2007, 17, 1237-1246;. . G Maier, polymers for Microelectronics [ polymers for microelectronics], materials today [materials today], Vol. 4, No. 5 , September-October 2001, 22-33; and PM Hergenrother, the use, design, synthesis, and properties of High Performance / High temperature polymers: uses an Overview [high performance / high temperature polymer, the design, synthesis and characterization : Review ] , High Performance Polymers [High Performance Polymers], 15: 3-45, 2003, Sage Publications [Sage Publications]. Suitable polymers include, for example, homopolymers or copolymers containing polymerized units of one or more of the following monomers, and may contain polymerized units of other monomers:

.

(B-1) 其中，在式 (B-1) 中，Ar¹ 、Z、x和*係如上關於式 (1) 定義的，並且前提係在該核的同一芳香族環上具有式 (B-1) 的取代基彼此不處於鄰位。該可固化化合物的B-階段反應產物可以藉由熟悉該項技術者已知的方法來製備。例如，化合物的B-階段化可以藉由將化合物溶解在合適的溶劑中來進行，該溶劑具有比B-階段化溫度更高的沸點。合適的溶劑包括例如以下關於塗層組成物的溶劑組分所述之那些。可能希望使用與稍後用於塗層組成物相同的溶劑用以B-階段化。B-階段化溶劑較佳的是選自丙二醇甲醚、丙二醇乙醚、丙二醇單甲醚乙酸酯、乳酸乙酯、γ-丁內酯、羥基異丁酸甲酯、環己酮、及其組合。溶液被加熱至一定溫度持續有效引起化合物的部分聚合或縮合的時間，直至達到目標分子量（Mw）。以上化合物的B-階段反應產物典型地具有400至50,000 Da、更較佳的是400至5,000 Da的重量平均分子量（Mw）。B-階段化溫度典型地是50°C至250°C、較佳的是100°C至200°C。B-階段化時間典型地是5分鐘至96小時、較佳的是2至24小時。已知的用於形成B-階段聚合物的方法例如描述於美國專利案號5,854,302和So, Y.-H等人,Benzocyclobutene -based polymers for microelectronics [ 用於微電子學的基於苯并環丁烯的聚合物 ] , Chemical Innovation [化學創新], 第31卷, 第12期, 第40-47頁 (2001) 中。Suitable B-stage polymers include the reaction products of curable compounds as described above. Therefore, in addition to the curable compound as described above, the coating composition may contain the same curable compound present in the composition or a B-stage reaction product of such a different curable compound as described above . For example, the B-stage reaction product may be a curable compound containing a core selected from the group consisting of a C ₆ carbocyclic aromatic ring, a C _2-5 heterocyclic aromatic ring, and a C _{9-30 condensed carbocyclic ring Aromatic ring} system, C _{4-30 fused heterocyclic aromatic ring} system, C _1-20 aliphatic, and C _3-20 alicyclic; and two or more attached to the nucleus having the formula ( Substituents of B-1):

(B-1) Wherein, in formula (B-1), Ar ¹ , Z, x and * are as defined above with respect to formula (1), and the premise is that the same aromatic ring of the nucleus has formula (B The substituents of -1) are not in the ortho position to each other. The B-stage reaction product of the curable compound can be prepared by a method known to those skilled in the art. For example, the B-staging of a compound can be performed by dissolving the compound in a suitable solvent that has a higher boiling point than the B-staging temperature. Suitable solvents include, for example, those described below with respect to the solvent component of the coating composition. It may be desirable to use the same solvent used for the coating composition later for B-staging. The B-staged solvent is preferably selected from propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, methyl hydroxyisobutyrate, cyclohexanone, and combinations thereof . The solution is heated to a certain temperature for a time effective to cause partial polymerization or condensation of the compound until the target molecular weight (Mw) is reached. The B-stage reaction product of the above compound typically has a weight average molecular weight (Mw) of 400 to 50,000 Da, more preferably 400 to 5,000 Da. The B-stage temperature is typically 50°C to 250°C, preferably 100°C to 200°C. The B-staging time is typically 5 minutes to 96 hours, preferably 2 to 24 hours. B- known methods for forming the polymer phase, for example, described in U.S. Patent Nos 5,854,302 and So, Y.-H, et al., Benzocyclobutene -based polymers for microelectronics [for microelectronics based benzocyclobutene The polymer ] , Chemical Innovation, Vol. 31, No. 12, pp. 40-47 (2001).

One or more polymers are typically present alone or in combination in an amount of, for example, 1 to 99 wt%, more typically 5 to 90 wt%, based on the total solids of the coating composition.

The coating composition includes one or more solvents for dissolving the components of the composition and facilitating its coating on the substrate. Preferably, the one or more solvents are selected from organic solvents conventionally used in the manufacture of electronic devices. Suitable organic solvents include, but are not limited to; hydrocarbons, such as xylene, mesitylene, cumene, and limonene; ketones, such as cyclopentanone, cyclohexanone (CHO), methyl ethyl ketone, And methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethyl Oxy-2-propanol; ethers, such as propylene glycol methyl ether (PGME), propylene glycol ethyl ether (PGEE), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol Dimethyl ether, anisole, and ethoxybenzene; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate (EL), methyl hydroxyisobutyrate (HBM ), ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tertiary butyl acetate, tertiary butyl propionate, propylene glycol mono tertiary butyl ether Acetate, benzyl propionate, cyclic or acyclic carbonates (such as propylene carbonate, dimethyl carbonate, ethylene carbonate, and diphenyl carbonate); lactones, such as γ-butyrolactone ( GBL); lactam, such as N-methylpyrrolidone; and any combination of the foregoing. Among them, the preferred solvents are PGME, PGEE, PGMEA, EL, HBM, CHO, GBL, and combinations thereof. The total solvent content (ie, the cumulative solvent content of all solvents) in the coating composition is based on 50 to 99 wt%, typically 80 to 99 wt%, and more typically 90 to 99 wt% of the coating composition. The desired solvent content will depend, for example, on the desired thickness of the applied base layer and the coating conditions.

The coating composition of the present invention may optionally contain one or more monomers, for example, one or more vinyl-containing monomers selected from (meth)acrylate monomers and vinyl aromatic monomers. The one or more monomers may contain one or more functional groups selected from, for example, hydroxyl, alkoxy, epoxy, alkenyl, alkynyl, carboxylic acid, acetal, ketal, tertiary alkyl ester, and amine . Among these functional groups, epoxy groups are particularly preferred. If present, such additive monomers may be present in the composition in a wide range such as 1 to 90 wt% based on the total solids of the coating composition.

The coating composition of the present invention may also contain one or more coating additives typically used in such coatings, such as curing agents, crosslinking agents, surface leveling agents, flow additives and the like. The selection of such optional additives and their amounts are completely within the capabilities of those skilled in the art. If used in the composition, the curing agent is typically present in an amount of 1 to 20 wt%, and preferably 1 to 3 wt% based on the total solids. If used, the crosslinking agent is typically present in an amount of 1 to 30 wt%, and preferably 3 to 10 wt%, based on total solids. If used, the surface leveling agent is typically used in an amount of 0.01 to 5 wt%, and preferably 0.01 to 1 wt%, based on the total solids. If used, the flow additive is typically used in an amount of 0.01 to 5 wt%, and preferably 0.01 to 3 wt%, based on total solids. The selection of such optional additives and their usage amount are within the ability of those familiar with the technology.

The curing agent may be used in the coating composition as needed to illustrate the curing of the composition after coating. The curing agent is any component that causes the composition to cure on the surface of the substrate. Preferred curing agents are acids and thermal acid generators. Suitable acids include, but are not limited to: arylsulfonic acids, such as p-toluenesulfonic acid; alkylsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid; perfluoroalkylsulfonic acids, such as trifluoro Methanesulfonic acid; and perfluoroarylsulfonic acid. A thermal acid generator is any compound that releases acid when exposed to heat. Thermal acid generators are well known in the art and are generally commercially available as from King Industries, Norwalk, Connecticut. Exemplary thermal acid generators include, but are not limited to, amine-terminated strong acids, such as amine-terminated dodecylbenzene sulfonic acid. Those skilled in the art will also understand that certain photoacid generators can release acid when heated and can be used as thermal acid generators.

(3)

(4)

(5)

(6)。Any suitable cross-linking agent can be used in the composition of the present invention, provided that such cross-linking agent has at least two, and preferably at least three, can interact with the present under suitable conditions (such as acidic conditions). The reaction part of the aromatic resin reaction product of the invention. Exemplary crosslinking agents include, but are not limited to, novolak resins, epoxy-containing compounds, melamine compounds, guanamine compounds, isocyanate-containing compounds, benzocyclobutene, etc., and preferably two or more of the foregoing Multiple, preferably 3 or more, and more preferably 4 are selected from epoxy, hydroxymethyl, C ₁ -C ₁₀ alkoxymethyl, and C ₂ -C ₁₀醯Any one of the substituents of oxymethyl. Suitable crosslinking agents are well known in the art and are commercially available from a variety of sources. Examples of suitable crosslinking agents include those of formula (3), (4), (5) and (6):

(3)

(4)

(5)

(6).

The coating composition of the present invention may optionally contain one or more surface leveling agents (or surfactants). Although any suitable surfactant can be used, such surfactants are typically nonionic. Exemplary nonionic surfactants are those containing alkyleneoxy linkages (such as ethyleneoxy, propyleneoxy, or a combination of ethyleneoxy and propyleneoxy linkages).

The coating composition of the present invention and the film formed therefrom can exhibit good gap filling, surface flattening, solvent stripping resistance and film quality characteristics. The composition of the present invention preferably substantially fills, and more preferably completely fills, a plurality of gaps in the semiconductor substrate. Preferably, the gap is substantially or completely void-free.

In the manufacture of electronic devices, an aromatic layer formed of the coating composition described herein can be formed according to a method, which includes: (a) providing an electronic device substrate; (b) coating the surface of the electronic device substrate with The layer of the coating composition as described herein; and (c) curing the layer of the curable compound to form a cured layer. The composition can be used as one or more of a photoresist bottom layer, a planarization layer, a gap filling layer, or a protective layer in the manufacture of electronic devices.

In an illustrative aspect of the present invention, a method for patterning a photoresist base layer using the coating composition of the present invention will be described. The method includes: (a) providing an electronic device substrate; (b) coating a layer of the coating composition as described herein on the surface of the electronic device substrate; (c) curing the layer of curable compound to form Bottom layer; (d) forming a photoresist layer on the bottom layer; (e) exposing the photoresist layer to activating radiation in a pattern; (f) developing the exposed photoresist layer To form a pattern in the photoresist layer; and (g) transfer the pattern to the bottom layer.

Suitable substrates on which the coating composition can be applied include electronic device substrates. A variety of electronic device substrates can be used in the present invention, such as: packaging substrates, such as multi-chip modules; flat panel display substrates; integrated circuit substrates; for light emitting diodes including organic light emitting diodes (OLED) ( LED) substrate; semiconductor wafer; polysilicon substrate; etc. Among them, semiconductor wafers are preferred. Such substrates are typically made of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Multiple composition. Suitable substrates may be in the form of wafers, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. As used herein, the term "semiconductor wafer" is intended to cover "semiconductor substrates", "semiconductor devices" and various packages for various interconnection levels, including single-chip wafers, multi-chip wafers, and Encapsulation, or other components that need to be soldered and connected. Such substrates can be of any suitable size. The preferred wafer base diameter is 200 mm to 300 mm, although wafers with smaller and larger diameters can be suitably used according to the present invention. As used herein, the term "semiconductor substrate" includes any substrate having one or more layers or structures, which may optionally include active or operable parts of a semiconductor device. A semiconductor device refers to a semiconductor substrate on which at least one microelectronic device has been mass-produced or is being mass-produced.

If necessary, an adhesion promoter layer can be applied to the surface of the substrate before applying the coating composition of the present invention. If the adhesion promoter is desired, any suitable adhesion promoter for the polymer film can be used, such as silane, preferably organosilane such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyl Disilazane, or aminosilane coupling agent such as γ-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those available from DuPont Electronics & Imaging (Marlborough, Massachusetts) sold under the names AP 3000, AP 8000, and AP 9000S Of those.

The coating composition of the present invention can be coated on the electronic device substrate by any suitable means such as spin coating, slot die coating, blade coating, curtain coating, roll coating, spray coating, dipping, etc. Among them, spin coating is preferable. In a typical spin coating method, the composition of the present invention is applied to a substrate rotating at a speed of 500 to 4000 rpm for a period of 15 to 90 seconds to obtain a desired coating composition layer on an electronic device substrate. Those skilled in the art will understand that the height of the coating composition layer can be adjusted by changing the rotation speed.

After the coating composition layer is applied to the substrate, it is baked at a relatively low temperature as necessary to remove any organic solvents and other relatively volatile components from the layer. Typically, the substrate is baked at a temperature of 80°C to 150°C, although other suitable temperatures can be used. The baking time is typically 10 seconds to 10 minutes, and preferably 30 seconds to 5 minutes, although longer or shorter times can be used. When the substrate is a wafer, this baking step can be performed by heating the wafer on a hot plate. After the solvent is removed, a layer, film or coating of the curable compound on the surface of the substrate is obtained.

Then, the curable compound layer is fully cured to form an aromatic underlayer under the following conditions, and the conditions are such that the film does not interact with subsequently applied coatings (such as a photoresist layer or other layers directly coated on the aromatic underlayer). ) Are mixed with each other while still maintaining the desired anti-reflection characteristics (n and k values) and etching selectivity of the underlying film. The bottom layer can be cured in an oxygen-containing atmosphere (such as air) or in an inert atmosphere (such as nitrogen), and preferably in an oxygen-containing atmosphere. This curing step is preferably performed on hot plate equipment, although oven curing can be used. Typically, this curing is performed by heating the bottom layer at a curing temperature of ≥ 150°C, preferably ≥ 170°C, and more preferably ≥ 200°C. The curing temperature and time selected should be sufficient to cure the aromatic bottom layer. The suitable temperature range for curing the aromatic base layer is 150°C to 400°C, preferably 170°C to 350°C, and more preferably 200°C to 250°C. This curing step can take 10 seconds to 10 minutes, preferably 1 to 3 minutes, and more preferably 1 to 2 minutes, although other suitable times may be used.

If the curing step is performed in such a way that the rapid release of solvent and curing by-products does not allow damage to the quality of the underlying film, the initial baking step may not be necessary. For example, a ramp-up bake that starts at a relatively low temperature and then gradually increases to a temperature ≥ 200°C can produce acceptable results. In some cases, it may be better to have a multi-stage curing process, such as a two-stage process, where the first stage is a lower baking temperature of less than 150°C, and the second stage is a higher temperature of ≥ 200°C. Baking temperature. The multi-stage curing process can promote the uniform filling and planarization of the pre-existing substrate surface topography, such as the filling of trenches and vias.

After curing the bottom layer, one or more processing layers, such as photoresist, silicon-containing layer, hard mask layer, bottom anti-reflective coating (or BARC) layer, etc., can be coated on the cured bottom layer. For example, the photoresist can be directly coated (such as by spin coating) on the surface of the silicon-containing layer or other intermediate layer directly on the resin bottom layer, or alternatively, the photoresist can be directly Coated on the cured bottom layer. A wide variety of photoresists can be used as appropriate, such as those used for 193 nm lithography, such as those available from DuPont Electronics and Imaging (Maruburg, Massachusetts) sold under the Epic™ brand Those ones. Suitable photoresists can be positive or negative. After coating, the photoresist layer is then imaged (exposed) using patterned activating radiation, and then the exposed photoresist layer is developed using a suitable developer to provide a patterned photoresist Floor. The exposure of the photoresist layer to activating radiation mentioned herein indicates that the radiation can form a latent image in the photoresist layer. The photoresist layer can be exposed to activating radiation by a patterned photomask with optically opaque and optically transparent regions or by direct writing. Next, the pattern is transferred from the photoresist layer to the bottom layer by a suitable etching technique. Typically, the photoresist is also removed during this etching step. Next, the pattern is transferred to the substrate and the bottom layer is removed by a suitable etching technique known in the art (such as by plasma etching). After patterning the substrate, the bottom layer is removed using conventional techniques. The electronic device substrate is then processed according to conventional means.

The cured bottom layer can be used as the bottom layer of a multilayer resist process. In this process, a layer of the coating composition is applied to the substrate and cured as described above. Next, one or more intermediate layers are coated on the aromatic bottom layer. For example, a silicon-containing layer or a hard mask layer can be directly coated on the aromatic base layer. An exemplary silicon-containing layer such as silicon-BARC can be deposited on the bottom layer by spin coating and then cured, or an inorganic silicon layer such as SiON or SiO can be deposited on the bottom layer by chemical vapor deposition (CVD). Any suitable hard mask can be used and can be deposited on the bottom layer by any suitable technique and cured (where appropriate). If necessary, the organic BARC layer can be directly placed on the silicon-containing layer or the hard mask layer and cured appropriately. Next, the photoresist (such as those used in 193 nm lithography) is directly coated on the silicon-containing layer (in the three-layer process) or directly on the organic BARC layer (in the four-layer process) middle). The photoresist layer is then imaged (exposed) using patterned activating radiation, and the exposed photoresist layer is then developed using a suitable developer to provide a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the layer directly below it by a suitable etching technique known in the art (such as by plasma etching). This produces a patterned silicon-containing layer in a three-layer process and a patterned organic BARC layer in a four-layer process. If a four-layer process is used, then an appropriate pattern transfer technique (such as plasma etching) is used to transfer the pattern from the organic BARC layer to the silicon-containing layer or hard mask layer. After patterning the silicon-containing layer or the hard mask layer, an appropriate etching technique (such as O ₂ or CF ₄ plasma) is then used to pattern the aromatic base layer. During the etching of the aromatic bottom layer, any remaining patterned photoresist layer and organic BARC layer are removed. Next, if the pattern is transferred to the substrate by an appropriate etching technique, this also removes any remaining silicon-containing layer or hard mask layer, and then removes any remaining patterned aromatic underlayer to provide a patterned Base.

The cured bottom layer of the present invention can also be used in a self-aligned double patterning process. In this process, it is preferable to coat the coating composition layer of the present invention on the substrate by spin coating. Any remaining organic solvent is removed and the coating composition layer is cured to form a cured underlayer. A suitable intermediate layer, such as a silicon-containing layer, is coated on the cured bottom layer. Then, a suitable photoresist layer is coated on the intermediate layer, such as by spin coating. The photoresist layer is then patterned (exposed) with activating radiation, and then the exposed photoresist layer is developed using a suitable developer to provide a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the intermediate layer and the cured bottom layer by a suitable etching technique to expose a part of the substrate. Typically, the photoresist is also removed during this etching step. Next, a conformal silicon-containing layer is placed on the patterned cured bottom layer and exposed portions of the substrate. Such a silicon-containing layer is typically an inorganic silicon layer conventionally deposited by CVD, such as SiON or SiO ₂ . This type of conformal coating produces a silicon-containing layer on the exposed portion of the substrate surface and on the underlying pattern. In other words, this silicon-containing layer basically covers the sides and top of the patterned bottom layer. Next, the silicon-containing layer is partially etched (trimmed) to expose the top surface of the patterned polyarylene resin bottom layer and a part of the substrate. After this partial etching step, the pattern on the substrate contains multiple features, each feature contains a line or column for the cured bottom layer, where the silicon-containing layer is directly adjacent to the side of each cured bottom layer feature, also called sidewall spacers . Next, the cured bottom layer is removed by etching, so that the surface of the substrate under the cured bottom layer pattern is exposed, and a patterned silicon-containing layer is provided on the substrate surface, which is similar to the patterned cured bottom layer. Compared with this type of patterned silicon-containing layer is double (ie, twice as many lines and/or pillars).

In addition to their use in forming the photoresist underlayer and pattern as described above, the coating composition of the present invention can be used to form a planarization layer, a gap filling layer and a protective layer in the manufacture of integrated circuits. When used as such a layer, one or more intervening material layers (such as silicon-containing layers, other aromatic resin layers, hard mask layers, etc.) are typically present in the cured layer of the coating composition of the present invention and any Between the photoresist layers. Typically, such a planarization layer, gap filling layer, and protective layer are finally patterned.

The following non-limiting examples illustrate the invention. Example Synthesis Example Synthesis Example A

合成實例BAdd 4-iodophenylacetate (24.75 g), cuprous iodide (0.17 g), and triethylamine (27.32 g) to 22.82 g of 1,4-Di㗁𠮿 at room temperature. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (0.63 g) was added to the reaction mixture, and the mixture was heated to 70°C. Then a solution of 1,3,5-triethynylbenzene (4.5 g) in degassed 1,4-diacetylene (20 g) was slowly added to the reaction mixture by means of a syringe pump. After the addition was complete, the reaction mixture was stirred at 70°C under nitrogen overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solvent was evaporated. The residue was diluted with ethyl acetate and filtered to remove solids. The solution was evaporated, and the residue was purified by column chromatography to obtain a pale yellow solid. The obtained solid was then dissolved in THF (38 g) under nitrogen. Lithium hydroxide monohydrate (3.81 g) and water (16 g) were added, and the mixture was stirred at 60°C for 1 hour. The mixture was then cooled to room temperature, and the solvent was removed. The residue was diluted with ethyl acetate and water, and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to obtain 1,3,5-tris((4-hydroxyphenyl)ethynyl)benzene (7.7 g, 61%) as a pale yellow solid Yield). The reaction is shown in Reaction Scheme 1.

Synthesis Example B

合成實例CAdd 5,5'-oxybis(1,3-dibromobenzene) (3.61 g), cuprous iodide (0.21 g) and triethylamine (3.42 g) to 20 g of 1, 4- Two 㗁𠮿 in. The reaction mixture was purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium(II) chloride (0.53 g) was added to the reaction mixture, and the mixture was heated to 70°C. 4-ethynyl phenyl acetate (4.81 g) was dissolved in degassed 1,4-diacetyl (17 g), and then the solution was slowly added to the reaction mixture through an addition funnel. After the addition was complete, the reaction mixture was stirred at 70°C under nitrogen overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered, and the solvent was evaporated. The residue was purified by chromatography to obtain a pale yellow solid. The obtained solid was then dissolved in THF (40 g) under nitrogen. Lithium hydroxide monohydrate (1.26 g) and water (10 g) were added, and the mixture was stirred at 60°C for 1 hour. The reaction mixture was then diluted with ethyl acetate, and then treated with hydrochloric acid until the pH of the aqueous layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to obtain 5,5'-oxybis(1,3-bis((4-hydroxyphenyl)ethynyl) as a pale yellow solid Benzene) (3.1 g, 65% yield). The reaction is shown in Reaction Scheme 2.

Synthesis Example C

合成實例D1,3,5-tris((4-hydroxyphenyl)ethynyl)benzene (6.0 g) in dry DMF (46 g) was stirred at room temperature for 15 minutes. The mixture was heated to 30°C and then K ₂ CO ₃ (10.34 g) was added. The reaction mixture was heated to 50°C and a solution of 8.63 g bromopropyne (80% in toluene) was added dropwise via the addition funnel. Maintain the temperature at 50°C for 24 hours. The reaction mixture was then cooled to room temperature and filtered to remove most of the K ₂ CO ₃ . The organics were precipitated into 2 L of water and stirred at room temperature for 0.5 hours. The precipitated polymer was collected by filtration to provide a pale yellow solid product (5.8 g, 76% yield). The reaction is shown in Reaction Scheme 3.

Synthesis example D

合成實例EThe three-necked 50 mL round bottom flask is equipped with a mechanical stirrer, thermowell and condenser with nitrogen inlet. Fill the flask with 1-pyrenol (10.0 g), 2-naphthaldehyde (7.2 g) and PGME (40 mL). The reaction mixture was then stirred at room temperature under nitrogen. A clear solution was obtained after 30 minutes, and methanesulfonic acid (2.2 g) was added to the reaction mixture. The reaction mixture was heated to 120°C for 4 hours to provide a concentrated solution. The reaction mixture was then cooled to room temperature. The mixture was added to 400 mL methanol and water (v/v = 4/1), resulting in a gray precipitate. The precipitated resin was filtered with a Buchner funnel and dried under vacuum at 70° C. to obtain a gray solid resin (11.3 g, Mw = 1229). The reaction is shown in Reaction Scheme 4.

Synthesis Example E

合成實例F1,3,5-Tris((4-hydroxyphenyl)ethynyl)benzene (50 g), material A, and PGMEA (72 g) were added to a 250 mL round bottom flask. Nitrogen was charged to the flask, and the reaction mixture was stirred at room temperature until all solids were dissolved. The solution was then heated to 140°C. The mixture was cooled to room temperature and diluted with PGMEA (45 g). The resulting solution was then filtered through a 0.2 micron PTFE filter to produce B-stage material E (Mw=1550). The reaction is shown in Reaction Scheme 5.

Synthesis example F

底層組成物製備 實例1-26Combine 30.0 g 3,3′-(oxydi-1,4-phenylene) bis(2,4,5-triphenylcyclopentadienone), 18.1 g 1,3,5-tris(benzene A mixture of phenylethynyl)benzene and 102.2 g γ-butyrolactone was heated at 185°C for 14 hours. The reaction was then cooled to room temperature and diluted with 21.5 g GBL. The crude reaction mixture was added to 1.7 L of a 1:1 mixture of IPA/PGME and stirred for 30 minutes. The solid was collected by vacuum filtration and washed with a 1:1 mixture of IPA/PGME. 0.4 L of water was added to the solid, and the slurry was heated to 50°C and stirred at 50°C for 30 minutes. The warm slurry was filtered by vacuum filtration. The wet cake was vacuum dried at 70°C for 2 days, resulting in a polymer (34.1 g, 71% yield, Mw = 3588, PDI = 1.38). The reaction is shown in Reaction Scheme 6.

Bottom composition preparation Examples 1-26

The material prepared as in the synthesis example (including any added solvents) was added to the mixture of PGMEA/benzyl benzoate (97/3 by weight after addition of the polymer and comparative material composition) to form a composition with about 5 wt% total solids solution. The other components, if any, were combined with the solution to provide a base composition formulation having the relative amounts of the components described in Table 1. [Table 1] Instance Bottom composition Curable compound Solvent polymer Crosslinking agent 1 UC-1 A (1.485) PB (95.0) D (3.465) MF (0.05) 2 UC-2 A (0.925) PB (95.0) D (3.700) HM (0.375) 3 UC-3 B (0.925) PB (95.0) D (3.700) HM (0.375) 4 UC-4 A (0.925) PB (95.0) S275 (3.7) HM (0.375) 5 UC-5 B (0.925) PB (95.0) S275 (3.7) HM (0.375) 6 UC-6 A (1.0) PB (95.0) PHS (4.0) - 7 UC-7 A (0.925) PB (95.0) PHS (3.7) HM (0.375) 8 UC-8 A (1.0) PB (95.0) MA (4.0) - 9 UC-9 A (0.925) PB (95.0) GMA (3.7) HM (0.375) 10 UC-10 A (1.0) PB (95.0) GMA (4.0) - 11 UC-11 A (2.0) PB (95.0) GMA (3.0) - 12 UC-12 A (3.0) PB (95.0) GMA (2.0) - 13 UC-13 A (4.0) PB (95.0) GMA (1.0) - 14 UC-14 A (1.0) PB (95.0) E (4.0) - 15 UC-15 A (2.0) PB (95.0) E (3.0) - 16 UC-16 A (3.0) PB (95.0) E (2.0) - 17 UC-17 C (1.5) PB (95.0) F (3.5) - 18 (comparison) UC-18 - PB (95.0) D (4.95) MF (0.05) 19 (comparison) UC-19 - PB (95.0) D (4.625) HM (0.375) 20 (contrast) UC-20 - PB (95.0) S275 (4.625) HM (0.375) 21 (comparison) UC-21 - PB (95.0) PHS (5.0) - 22 (comparative) UC-22 - PB (95.0) PHS (4.625) HM (0.375) 23 (comparison) UC-23 - PB (95.0) MA (5.0) - 24 (contrast) UC-24 - PB (95.0) GMA (4.625) HM (0.375) 25 (contrast) UC-25 - PB (95.0) GMA (5.0) - 26 (contrast) UC-26 - PB (95.0) F (5.0) -

*The content of curable compounds, polymers and other solid materials does not include solvents; GMA = polyglycidyl methacrylate (Miwon Commercial Co., Ltd.); MF = MODAFLOW acrylic resin (Netherlands Allnex Netherlands BV); HM = hexa(methoxymethyl) melamine (Nihon Cytec Industries Inc.); S275 = 1-naphthol/formaldehyde novolac polymer (group Gun-Ei chemical; PHS = poly(4-hydroxystyrene) Mw 5000 (Toyota Tsusho America, Inc.); MA = hydroxyethyl methacrylate/methyl Copolymer of methyl acrylate 40/60 (St. Jean Photochemicals); PB = PGMEA/benzyl benzoate (97/3 by weight after addition of materials and comparative material composition); The component values are based on the wt% solids of the total bottom layer composition. Evaluation of Solvent Peeling Resistance Example 1-26

Each composition was spin-coated on the corresponding 200 mm silicon wafer at 1500 rpm on the ACT-8 Clean Track (Tokyo Electron Co.), and then the temperature and time listed in Table 2 Cure down to form a film. Use Therma-Wave OptiProbe™ metrology tool to measure the initial film thickness. Then the PGMEA remover was applied to each film for 90 seconds, followed by post-peeling at 105°C for 60 seconds. The thickness of each film was measured again to determine the amount of film thickness loss. The difference in film thickness before and after contact with the PGMEA remover is listed in Table 2 as a percentage of the remaining film thickness on the wafer (% remaining film). This value indicates the degree of crosslinking of the polymer layer. [Table 2] Instance Bottom composition Curing temperature / time % Remaining film 1 UC-1 350°C/60 s ＞ 99% 2 UC-2 300°C/60 s ＞ 99% 3 UC-3 300°C/60 s ＞ 99% 4 UC-4 240°C/60 s ＞ 99% 5 UC-5 240°C/60 s ＞ 99% 6 UC-6 300°C/60 s ＞ 99% 7 UC-7 240°C/60 s ＞ 99% 8 UC-8 300°C/60 s 95% 9 UC-9 240°C/60 s ＞ 99% 10 UC-10 220°C/60 s ＞ 99% 11 UC-11 220°C/60 s ＞ 99% 12 UC-12 220°C/60 s ＞ 99% 13 UC-13 220°C/60 s 86% 14 UC-14 220°C/60 s ＞ 99% 15 UC-15 220°C/60 s ＞ 99% 16 UC-16 220°C/60 s ＞ 99% 17 UC-17 350°C/90 s ＞ 99% 18 (comparison) UC-18 350°C/60 s 85% 19 (comparison) UC-19 300°C/60 s 64% 20 (contrast) UC-20 240°C/60 s ＞ 99% 21 (comparison) UC-21 300°C/60 s 3% 22 (comparative) UC-22 240°C/60 s 89% 23 (comparison) UC-23 300°C/60 s 5% 24 (contrast) UC-24 240°C/60 s 4% 25 (contrast) UC-25 220°C/60 s ＜5% 26 (contrast) UC-26 350°C/90 s ＜ 10% Gap Filling and Flattening Evaluation Examples 27-41

A 300 mm silicon wafer with various patterning features was used to evaluate the gap filling and planarization performance of the underlying composition. These features are formed in a 100 nm thick PECVD silicon oxide layer coated on the wafer. Before coating the composition, the wafer is dehydrated and baked at 150°C for 60 seconds. Using ACT-8 Clean Track (Tokyo Electronics Co., Ltd.), each composition was coated on the corresponding wafer at 1300-1700 rpm to achieve the target film thickness of approximately 100 nm after curing. The coated composition was cured under the temperature and time conditions in Table 3 by placing the wafer on a hot plate. The cross-sectional image was taken on Hitachi High Technology S4800 CD-SEM.

The SEM image was used to evaluate the gap filling performance by visually inspecting the 45 nm 1:1 (90 nm pitch) line/space pattern coated with the bottom layer. If no voids or bubbles are observed, it is considered that the gap filling performance is good. The bottom layer-coated groove pattern (2 μm-wide interval defined between 3 μm-wide lines) was used to evaluate the planarization performance of the bottom-layer composition. The KLA Tencor P-7 stylus profiler measures the height difference between the maximum height (on the groove line pattern) and the minimum height (on the groove interval) of the bottom layer. An underlayer with a height difference of 260 Å or less is considered to have good planarization and a film with a height difference of more than 260 Å is considered to have poor planarization. The results are listed in Table 3. [table 3] Instance Bottom composition Curing temperature / time Gap filling flattened 27 UC-1 350°C/60 s. good good 28 UC-6 300°C/60 s. good good 29 UC-7 240°C/60 s. good good 30 UC-8 300°C/60 s. good good 31 UC-9 240°C/60 s. good good 32 UC-10 220°C/60 s. good good 33 UC-11 220°C/60 s. good good 34 UC-14 220°C/60 s. good good 35 UC-15 220°C/60 s. good good 36 UC-16 220°C/60 s. good good 37 UC-17 350°C/90 s. good good 38 (contrast) UC-18 350°C/60 s. good Difference 39 (contrast) UC-19 300°C/60 s. good Difference 40 (contrast) UC-20 240°C/60 s. good Difference 41 (comparative) UC-26 350°C/90 s. good Difference Coating quality evaluation example 42-63

The bottom layer composition was spin-coated on a corresponding 200 mm silicon wafer at 1500 rpm on the ACT-8 Clean Track (Tokyo Electronics Co., Ltd.), and then cured under the temperature and time conditions in Table 4 to form a bottom layer film. The coating quality was evaluated by visually inspecting the film with both the naked eye and an optical microscope. If any streaks or dewetting are observed, the coating quality is judged to be of poor quality, and if they are not present, it is of good quality. The results are reported in Table 4. [Table 4] Instance Bottom composition Curing temperature / time Coating quality 42 UC-1 350°C/60 s good 43 UC-2 300°C/60 s good 44 UC-3 300°C/60 s good 45 UC-4 240°C/60 s good 46 UC-5 240°C/60 s good 47 UC-6 300°C/60 s good 48 UC-7 240°C/60 s good 49 UC-8 300°C/60 s good 50 UC-9 240°C/60 s good 51 UC-14 220°C/60 s. good 52 UC-15 220°C/60 s. good 53 UC-16 220°C/60 s. good 54 UC-17 350°C/90 s good 55 (contrast) UC-18 350°C/60 s good 56 (contrast) UC-19 300°C/60 s good 57 (contrast) UC-20 240°C/60 s good 58 (comparative) UC-21 300°C/60 s good 59 (contrast) UC-22 240°C/60 s good 60 (contrast) UC-23 300°C/60 s good 61 (comparative) UC-24 240°C/60 s good 62 (comparative) UC-25 220°C/60 s good 63 (comparative) UC-26 350°C/90 s good

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Claims (16)

A coating composition comprising: a first curable compound, the first curable compound comprising: a core selected from the group consisting of a C ₆ carbocyclic aromatic ring, a C _2-5 heterocyclic aromatic ring, and a C _{9- 30 fused carbocyclic aromatic ring} system, C _{4-30 fused heterocyclic aromatic ring} system, C _1-20 aliphatic, and C _3-20 alicyclic; and three or more of the formula (1 ) Substituents

(1) wherein at least two substituents having formula (1) are attached to the core; and wherein: Ar ^{1 is} selected from C ₆ carbocyclic aromatic ring, C _2-5 heterocyclic aromatic ring, C _9-30 Condensed carbocyclic aromatic ring system, and C _4-30 condensed heterocyclic aromatic ring system; Z is independently selected from the following substituents: OR ¹ , protected hydroxyl, carboxy, protected carboxy, SR ^1. Protected mercapto, -OC(=O)-C _1-6 alkyl, halogen, and NHR ² ; wherein each R ^{1 is} independently selected from H, C _1-10 alkyl, C _2-10 Saturated hydrocarbon group, and C _5-30 aryl group; each R ^{2 is} independently selected from H, C _1-10 alkyl group, C _2-10 unsaturated hydrocarbon group, C _5-30 aryl group, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x is an integer from 1 to the ^{total number of aromatic ring atoms available in Ar 1} ; and * indicates the point of attachment to the nucleus; the premise is on the same aromatic ring of the nucleus The above substituents with formula (1) are not in the ortho position to each other; polymers; and one or more solvents, wherein the total solvent content is based on 50 to 99 wt% of the coating composition. The coating composition according to claim 1, wherein the polymer is selected from the group consisting of acrylate, vinyl aromatic polymer, novolac, polyphenylene, polyimide, polybenzoxazole, and polyphenylene Bisimidazole, polyether stubble, and combinations thereof. The coating composition according to claim 2, wherein the polymer is selected from acrylate, vinyl aromatic polymer, novolac, polyphenylene, and combinations thereof. The coating composition according to claim 1, wherein the polymer is a B-stage reaction product of a second curable compound, and the second curable compound comprises: a core selected from the group consisting of C ₆ carbocyclic aromatics Ring, C _2-5 heterocyclic aromatic ring, C _{9-30 fused carbocyclic aromatic ring} system, C _{4-30 fused heterocyclic aromatic ring} system, C _1-20 aliphatic, and C _3-20 Cycloaliphatic; and two or more substituents of formula (B-1) attached to the core:

(B-1) Wherein in formula (B-1): Ar ^{1 is} selected from C ₆ carbocyclic aromatic ring, C _2-5 heterocyclic aromatic ring, C _9-30 condensed carbocyclic aromatic ring system, And C _4-30 fused heterocyclic aromatic ring system; Z is independently selected from the following substituents: OR ¹ , protected hydroxyl, carboxy, protected carboxy, SR ¹ , protected sulfhydryl, -OC (=O)-C _1-6 alkyl, halogen, and NHR ² ; wherein each R ^{1 is} independently selected from H, C _1-10 alkyl, C _2-10 unsaturated hydrocarbon group, and C _5-30 aromatic Group; each R ^{2 is} independently selected from H, C _1-10 alkyl, C _2-10 unsaturated hydrocarbon group, C _5-30 aryl, C(=O)-R ¹ , and S(=O) ₂ -R ¹ ; x is an integer from 1 to the ^{total number of aromatic ring atoms available in Ar 1} ; and * indicates the point of attachment to the nucleus; the premise is that the nucleus has the formula (B-1) on the same aromatic ring The substituents are not in the ortho position to each other. The coating composition according to any one of claims 1 to 4, wherein each Z in formula (1) is independently selected from OR ¹ , a protected hydroxyl group, a carboxyl group, a protected carboxyl group, SH, -OC(=O)-C _1-6 alkyl, and NHR ² . The coating composition according to claim 5, wherein each Z in the formula (1) is a hydroxyl group. The coating composition according to any one of claims 1 to 6, wherein the core of the first curable compound is selected from the group consisting of pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene , Benzophenanthrene, chrysene, anthracene, benzo[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene. The coating composition according to any one of claims 1 to 7, wherein each Ar ¹ in formula (1) is independently selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene , Pyrene, coronene, triphenanthrene, chrysene, anthracene, benzo[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene. The coating composition according to any one of claims 1 to 8, which further comprises a curing agent, a surface leveling agent, or a flow additive. The coating composition according to any one of claims 1 to 9, which further comprises a crosslinking agent which is different from the first curable compound and the polymer. A coated substrate, which includes: Electronic device substrate; and A layer formed of the coating composition according to any one of claims 1 to 10 on the surface of the electronic device substrate. A method of forming an electronic device, which includes: (a) Provide electronic device substrate; (b) Coating the layer of the coating composition according to any one of claims 1 to 10 on the surface of the electronic device substrate; and (c) curing the layer of the curable compound to form a cured layer. The method according to claim 12, wherein the cured layer is a photoresist bottom layer, and the method further comprises: (d) A photoresist layer is formed on the bottom layer; (e) Expose the photoresist layer to activating radiation in a pattern; (f) Develop the exposed photoresist layer to form a pattern in the photoresist layer; and (g) Transfer the pattern to the bottom layer. The method according to claim 13, further comprising coating one or more of a silicon-containing layer, an organic anti-reflection coating, or a combination thereof on the bottom layer before step (d). The method according to claim 14, further comprising, after step (f) and before step (g), transferring the pattern to one or more of the silicon-containing layer, the organic anti-reflective coating, or a combination thereof Up. The method according to any one of claims 13 to 15, which further includes: (h) Transfer the pattern to the layer of the electronic device substrate under the patterned bottom layer; and (i) Remove the patterned bottom layer.